@phdthesis{Haubitz2021,
  author    = {Haubitz, Toni},
  title     = {Transient absorption spectroscopy},
  doi       = {10.25932/publishup-53509},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-535092},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xiii, 176},
  year      = {2021},
  abstract  = {The optical properties of chromophores, especially organic dyes and optically active inorganic molecules, are determined by their chemical structures, surrounding media, and excited state behaviors. The classical optical go-to techniques for spectroscopic investigations are absorption and luminescence spectroscopy. While both techniques are powerful and easy to apply spectroscopic methods, the limited time resolution of luminescence spectroscopy and its reliance on luminescent properties can make its application, in certain cases, complex, or even impossible. This can be the case when the investigated molecules do not luminesce anymore due to quenching effects, or when they were never luminescent in the first place. In those cases, transient absorption spectroscopy is an excellent and much more sophisticated technique to investigate such systems. This pump-probe laser-spectroscopic method is excellent for mechanistic investigations of luminescence quenching phenomena and photoreactions. This is due to its extremely high time resolution in the femto- and picosecond ranges, where many intermediate or transient species of a reaction can be identified and their kinetic evolution can be observed. Furthermore, it does not rely on the samples being luminescent, due to the active sample probing after excitation. In this work it is shown, that with transient absorption spectroscopy it was possible to identify the luminescence quenching mechanisms and thus luminescence quantum yield losses of the organic dye classes O4-DBD, S4-DBD, and pyridylanthracenes. Hence, the population of their triplet states could be identified as the competitive mechanism to their luminescence. While the good luminophores O4-DBD showed minor losses, the S4-DBD dye luminescence was almost entirely quenched by this process. However, for pyridylanthracenes, this phenomenon is present in both the protonated and unprotonated forms and moderately effects the luminescence quantum yield. Also, the majority of the quenching losses in the protonated forms are caused by additional non-radiative processes introduced by the protonation of the pyridyl rings. Furthermore, transient absorption spectroscopy can be applied to investigate the quenching mechanisms of uranyl(VI) luminescence by chloride and bromide. The reduction of the halides by excited uranyl(VI) leads to the formation of dihalide radicals X^(·-2). This excited state redox process is thus identified as the quenching mechanism for both halides, and this process, being diffusion-limited, can be suppressed by cryogenically freezing the samples or by observing these interactions in media with a lower dielectric constant, such as ACN and acetone.},
  language  = {en}
}